1. Field of the Invention
The present invention relates to novel thiazole derivatives, which have insecticidal and acaricidal activity. The preparation and use, in agriculture and horticulture, of agrochemical compositions containing these novel insecticidal thiazoles are also disclosed.
2. Description of the Related Art
It is known in the art that certain thiazole derivatives such as those disclosed in U.S. Pat. Nos. 4,199,506, 4,284,426, 4,371,389, 4,437,875 and 4,437,876 have herbicide antidote properties and in Japan Kokai Koho 06-25199 have fungicidal properties. Furthermore, it is known in the art that UK patent application GB 2331748 discloses 5-cyano or thiocarbamoyl thiazole derivatives and their use as insecticides, acaricides or nematocides. The present invention concerns the novel thiazole derivatives which have excellent insecticidal and acaricidal activity.
In accordance with the present invention, thiazole derivatives are provided having the formula (1): 
wherein
R1 is CN or fluoroalkyl,
R2 is H, halogen or CN,
R3 is aryl, phenylalkyl, alkyl, cycloalkyl groups ( being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), alkylthiocarbamoyl, or aroyl (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), arylthiocarbonyl (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), aryl or alkylsulfonyl (being optionally substituted by one or more of halogen),
R4 is aryl (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy).
X is O, SOn, n is 0, 1 or 2.
or X is N(R5) wherein,
R3 and R5 are, independently, H or alkyl, alkoxy, acyl, alkylamino, aryl groups (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), or arylamino (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), or R3 and R5 may additionally be fused to a heteroaromatic ring.
The present invention is directed to agrochemical compositions comprising as an active ingredient at least one of the novel thiazole derivatives of the present invention, as well as to the use of these active ingredients or compositions for pest control, and, in particular as insecticides and acaricides useful in agriculture and horticulture.
For a better understanding of the present invention, reference is made to the following description and its scope will be pointed out in the appended claims.
For purposes of the present invention the general terms used hereinabove and hereinbelow have the following meanings, unless otherwise defined:
Alkyl groups are, in accordance with the number of carbon atoms, straight-chain or branched and will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, 1-hexyl, or 3-hexyl.
Cycloalkyl groups are generally cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
Halogen and halo substituents will be understood generally as meaning fluoro, chloro, bromo, iodo. chloro, bromo, or iodo are preferred meanings in this invention.
Haloalkyl can contain identical or different halogenatoms, typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, trichloromethyl Fluoroalkyl is generally fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, n-heptafluoroprpyl, n-nonafluorobutyl, n-undecafluoropentyl, n-tridecafluorohexyl and preferably trifluoromethyl and pentafluoroethyl.
Alkoxy is typically methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy, methoxy and ethoxy are preferred.
Aryl is typically substituted phenyl or naphthyl, furyl, thienyl, six-membered heteroaromatic ring system such as pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl (1,2,3-, 1,2,4- and 1,3,5-), quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, indolinyl, isoindolinyl, five membered heteroaromatic ring such as thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyrazolyl, thiadiazolyl oxadiazolyl, pyrollyl, imidazolyl, triazolyl (1,2,3- and 1,2,4-), tetrazolyl, fused five membered rings such as benzofuranyl, benzothienyl, benzimidazolinyl; being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy.
Aroyl is typically substituted benzoyl; being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy.
Alkenyl and alkynyl groups preferably contain from 2 to 6, more preferably from 2 to 4, carbon atoms. They can be in the form of straight or branched chains, and, where appropriate, the alkenyl groups can be of either (E)- or (Z)- configuration. Examples are vinyl, allyl, propargyl.
The alkylenedioxy groups are optionally substituted with halogene (especially fluorine) and are such as methylenedioxy or difluoromethylenedioxy.
The present invention provides the use as insecticides or acaricides of thiazole derivatives having the following formula (1): 
wherein
R1 is CN or fluoroalkyl (especially C1-C4 fluoroalkyl),
R2 is H, halogen or CN,
R3 is aryl, phenylalkyl, alkyl, cycloalkyl groups (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), alkylthiocarbamoyl, or aroyl (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy),
R4 is aryl (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy).
X is O, SOn, n is 0, 1 or 2.
or X is N(R5) wherein,
R3 and R5 are, independently, H or alkyl, alkoxy, acyl, alkylamino, aryl groups (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), or arylamino (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), or R3 and R5 may additionally be fused to a heteroaromatic ring.
Examples of specific compounds of formula (1), which are of use as insecticides and acaricides include the compounds listed in Table I at end of this disclosure. NMR data of oily substances in the formula 1 are shown in Table 2, which also follows at the end of this disclosure.
The present invention also provides a process for the preparation of a compound of (1) as defined above which comprises
(a) reacting a compound of the general formula 
xe2x80x83in which R1, R2 and R4 are as defined above with phosphorous pentachloride and phosphorous oxychloride to produce the intermediate (3) 
(b) reacting a compound of the general formula (3) in which R1, R2 and R4 are as defined above with R3xe2x80x94Xxe2x80x94A in which X is O or S, R3 is defined above and A is an alkali metal radical such as Na or K, or R3xe2x80x94Xxe2x80x94H in which X is Nxe2x80x94R5 with an inorganic base such as NaH, NaOH, KOH, K2CO3, Na2CO3 or an organic amine such as pyridine, triethylamine, imidazole to produce (1).
(c) reacting a compound of the general formula (3) in which R1, R2 and R4 are as defined above with thiourea to produce the intermediate (4) followed by reacting an alkali metal salt of the general formula (4) with R3xe2x80x94Y in which R3 is alkyl, cycloalkyl groups (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy), alkylthiocarbamoyl, or aroyl 
xe2x80x83(being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy),
R4 is aryl (being optionally substituted by one or more of halogen, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkylamino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy) and
Y is halogen to produce (1) in which R1, R2 and R4 are defined above and X is S and R3 is as defined above.
The procedure of step (a) is carried out in the excess amount of phosphorous oxychloride without other solvents at the reflux temperature. The procedure of step (b) is conveniently carried out in the presence of a solvent. Suitable solvents include aprotic solvents such as benzene, acetone, methylethyl ketone, chloroform, acetonitrile, tetrahydrofuran, dioxane, DMSO, DMF at a temperature in the range from 0xc2x0 C. to a reflux temperature of the solvent. The procedure of step (c), formation of the compound of the general formula (4) is carried out in methanol, ethanol, tetrahydrofuran, dioxane, DMSO, DMF at a temperature range from 50xc2x0 C. to a reflux temperature of the solvent. The next procedure to the formation of a compound of the general formula (1) is carried out in tetrahydrofuran, dioxane, DMSO, DMF at a temperature range from 0xc2x0 C. to a reflux temperature of the solvent. Surprisingly, it has now been found that the novel compounds of formula (1) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against insect and acarine pests, include such as Coleoptera, Diabrotica, Diptera, Homoptera and Lepidoptera, Heteroptera, Thysanoptera, Orthoptera and Acarina. The pests include those pests associated with agriculture, horticulture and animal husbandry, forestry, the storage of products of vegetable origin, such as fruit, grain, and timber, and also those pests associated with the transmission of diseases of man and animals.
Examples of insect and acarine pest species which may be controlled by the compounds of formula (1) include: Pieris brassicae (white butterfly), Pseudaletia separata (rice armyworm), Heliothis virescens (tobacco budworm), Trialeurodes spp. (white flies), Aedes aegypti (mosquito), Agrotis spp. (cutworms), Blatta orientalis (cockroach), Anopheles spp. (mosquitos), Chilo partellus (maize stem borer), Culex spp. ((mosquitos), Dysdercus fasciatus (capsid), Musca domestica (housefly), Plutella xylostella (diamond back moth), Aonidiella spp. (scale insects), Bemisia tabaci (sweetpotato white fly), Blattella germanica (German cockroach), Myzus persicae (green peach aphid), Aphis gossypii (cotton aphid), Aphis fabae (bean aphid), Periplaneta americana (American cockroach), Phaedon cochleariae (mustard beetle), Spodoptera littoralis (cotton leafworm), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Nilaparvata lugens (brown rice planthopper), Nephotettix cincticeps (green rice leafhopper), Tetranychus cinnabarinus (carmine spider mite), Panonychus ulmi (European red mite), Phyllocoptruta oleivora (citrus rust mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Polyphagotarsonemus latus (brode mite) and Brevipalpus spp. (mites).
Compounds of the formula (1) are normally used in the form of compositions and can be applied to the crop or plant to be treated, simultaneously with or in succession with other compounds such as fertilizers, micronutrient donors or other preparations which influence the growth of plants. The thiazole derivatives of formula (1) can also be selectively combined with herbicides, as well as, other insecticides, fungicides, bactericides, nematocides, molluscicides or mixtures of several of these preparations and, if desired together with further carriers, surfactants or application promoting adjuvants employed in the art of formulation. In some cases, by mixing of the thiazole derivatives of formula (1) with other insecticides, results in synergistic insecticidal activity.
When applying the compound of the present invention in a practical way, the compound may be applied in a form as it is without adding other components. When the compound of the present invention is applied for plant protection purpose, the compound can be prepared into general types of formulations for plant protection use, such as wettable powder, granules, dust, emulsifiable concentrate, water soluble powder, suspension concentrate, flowable liquid, and so on.
In case the compound of the present invention is prepared into a solid type formulation, appropriate additives and carriers may be incorporated with the compound. Examples of the additive and the carrier include phytogenic powders, such as soybean powder and flour, mineral fine powders, such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay, and organic and inorganic compounds, such as sodium benzoate, urea and Glauber""s salt. In case the compound of the present invention is prepared into a liquid type formulation, an appropriate solvent is used for dissolving or dispersing the compound in the liquid type formulation. Examples of the solvent used for the liquid formulation include petroleum fractions, such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, methyl isobutyl ketone, mineral oils, vegetable oils and water.
In addition, in order to provide uniformity and stability to the compound in the prepared formulations, it is possible to add surface active agents into each formulation upon necessity. There is no limitation for the surface active agent, and examples of the surface active agent that can be added to the above-mentioned formulations include nonionic surface active agents, such as polyoxyethylene-added alkyl ether, polyoxyethylene-added higher fatty acid ester, polyoxyethylene-added sorbitan higher fatty acid ester and polyoxyethylene-added tristyryl phenyl ether, a sulfate ester of polyoxyethylene-added alkyl phenyl ether, an alkyl benzene sulfonate, a polycarbonate, a lignin sulfonate, a formaldehyde condensate of alkyl naphthalene sulfonate, and a copolymer of isobutylene and maleic anhydride.
In general, the content of an active ingredient in each of the formulations recited above is preferably in a range of from 0.01 to 90% by weight, and more preferably from 0.05 to 85% by weight based on the total weight of the formulation. Each of the prepared formulations, such as wettable powder, emulsifiable concentrate, suspension concentrate and flowable solution, is diluted with water to be prepared and adjusted into the suspension or emulsion with a desired concentration, and is applied to crop plants. For the formulations, such as granular and dust formulations, the formulation itself is directly applied to the target crop plants or soil.
Needless to say that the compound alone according to the present invention has sufficient insecticidal and acaricidal activity, however, it can be combined for the use with one or more of various types of other plant protection chemicals, for example, fungicides, insecticides, acaricides and synergists.
Hereunder, representative examples for fungicides, insecticides, acaricides and plant growth regulators those which can be combined to use with the compound according to the present invention will be recited below.
Fungicides:
Captan, Folpet, Thiuram, Ziram, Zineb, Maneb, Mancozeb, Propineb, Polycarbamate, Chlorothalonil, Quintozene, Captafol, Iprodione, Procymidone, Vinclozolin, Fluorimide, Cymoxanil, Mepronil, Flutolanil, Pencycuron, Oxycarboxine, Fosetyl aluminium, Propamocarb, Triadimefon, Triadimenol, Propiconazole, Diclobutrazol, Bitertanol, Hexaconazol, Microbutanil, Flusilazole, Etaconazole, Fluotrimazole, Flutriafen, Penconazole, Diniconazole, Cyproconazole, Fenarimol, Triflumizole, Prochloraz, Imazalyl, Pefurazoate, Tridemorph, Fenpropimorph, Triforine, Buthiobate, Pyrifenox, Anilazine, Polyoxins, Metalaxyl, Oxadixyl, Furalaxyl, Isoprothiolane, Probenazole, Pyrrolenitrine, Blastocidin-S, Kasugamycin, Balidamycin, Dihydrostreptomycin sulfate, Benomyl, Carbendazim, Thiophanate methyl, Hymexazol, Basic copper chloride, Basic copper sulfate, Fentin acetate, Triphenyltin hydroxide, Diethofencarb, Metasulfocarb, Quinomethionate, Binapacryl, Lecithin, Sodium hydrogencarbonate, Dithianone, Dinocap, Fenaminosulf, Diclomezine, GuazatineDodine, IBP, Edifenphos, Mepanipyrim, Ferimzone, Trichlamide, Metasulfocarb, Fluazinam, Ethoquinolac, Dimetomorph, Pyroquilon, Tecloftalam, Fthalide, Fenazine oxide, Thiabedazole, Tricyclazole, Vinclozolin, Cymoxanil, Cyclobutanil, Guaztine, Propamocarb hydrochloride, Oxolinic acid.
Insecticides and Acaricides:
Organophosphorous and carbamate insecticides: Fenthion, Fenitrothion, Diazinon, Chlorpyrifos, ESP, Vamidothion, Fenthoate, Dimethoate, Formothion, Malathion, Trichlorfon, Thiometon, Phosmet, Dichlorvos, Acephate, EPBP, Methyl parathion, Oxadimeton methyl, Ethion, Salithion, Cyanophos, Isoxathione, Pyridafenthion, Phosalone, Methidathion, Sulprofos, Chlorfevinphos, Tetrachlorvinphos, Dimethylvinphos, Propaphos, Isofenphos, Ethyl thiometon, Profenophos, Pyraclofos, Monocrotophos, Azinphos methyl, Aldicarb, Methomyl, Dithiocarb, Carbofuran, Carbosulfan, Benfuracarb, Furathiocarb, Propoxur, BPMC, MTMC, MIPC, carbaryl, Pyrimicarb, Ethiofencarb, Fenoxycarb, cartap, thiocyclam, bensultap, etc.
Pyrethroid insecticides: Permethrin, Cypermethrin, Deltamethrin, Fenvalerate, Fenpropathrin, Pyrethrin, Allethrin, Tetramethrin, Resmethrin, Dimethrin, Propathrin, Fenothrin, Prothrin, Fluvalinate, Cyfluthrin, Cyhalothrin, Flucythrinate, Ethofenprox, Cycloprothrin, Tralomethrin, Silafluofen, Brofenprox, Acrinathrin, etc.
Bezoyl urea and other insecticides: Diflubenzuron, Chlorfluazuron, Hexaflumuron, Triflumuron, Tetrabenzuron, Fulfenoxuron, Flucycloxuron, Buprofezin, Pyriproxyfen, Methoprene, Benzoepin, Diafenthiuron, Imidacloprid, Fipronyl, Nicotin sulfate, Rotenone, Metaldehyde, Machine oil, Microbial insecticides such as BT and insect-pathogenic viruses, etc.
NEMATICIDES: Fenamiphos, Fosthiazate, etc.
Acaricides:
Chlorbenzilate, Fenisobromolate, Dicofol, Amitraz, BPPS, Benzomate, Hexythiazox, Fenbutatin oxide, Polynactin, Quinomethionate, CPCBS, Tetradifon, Avermectin, Milbemectin, Clofentezin, Cyhexatin, Pyridaben, Fenpyroxymate, Tebufenpyrad, Pyrimidifen, Fenothiocarb, Dienochlor, etc.
Plant Groth Regulators: Gibberellins(e.g., Gibberellin A3, Gibberellin A4, Gibberellin A7), IAA, NAA, etc.